Siloxane-polyoxyalkylene block copolymers

ABSTRACT

THIS INVENTION RELATES TO THE USE OF MODIFIED SILOXANEPOLYOXYALKYLENE BLOCK COPOLYMER FOAM STABILIZERS IN THE PRODUCTION OF OPEN-CELL FLEXIBLE POLYETHER POLYURETHANE FOAM HAVING REDUCED FLAMMABILITY. THE BLOCK COPOLYMERS ARE MODIFIED WITH CERTAIN SILICON-BONDED ORGANIC GROUPS (E.G., C6H5CH2CH2- OR BICYLOHEPTYL GROUPS) WHICH INCREASE THE BULK SURFACE TENSION OF THE BLOCK COPOLYMERS. OPEN-CELL FLEXIBLE POLYETHER POLYURETHANE FOAMS ARE PRODUCED COMMERCIALLY FROM REACTION MIXTURES CONTAINING POLYURETHANE-FORMING REACTANTS, A CATALYST FOR THE REACTION OF THE POLYURETHANE-FORMING REACTANTS TO PRODUCE THE POLYURETHANE, A BLOWING AGENT AND A SILOXANEPOLYOXYALKYLENE BLOCK COPOLYMER FOAM STABILIZER. SUCH FOAMS ARE, TO SOME EXTENT, FLAMMABLE AND ARE USED IN APPLICATIONS (E.G., AUTOMOBILE SEAT CUSHIONS AND HOUSEHOLD FURNITURE CUSHIONS) WHERE FIRE CREATES A HAZARD. ACCORDINGLY, IT IS DESIRABLE TO REDUCE THE FLAMMABILITY OF SUCH FOAMS.

United States Patent 3,686,254 SILOXANE-POLYOXYALKYLENE BLOCK COPOLYMERS Edward L. Morehouse, New City, N.Y., assignor to Union Carbide Corporation, New York, N.Y. No Drawing. Filed Dec. 24, 1969, Ser. No. 888,067 Int. Cl. C07f U.S. Cl. 260448.7 B 7 Claims ABSTRACT OF THE DISCLOSURE This invention relates to the use of modified siloxanepolyoxyalkylene block copolymer foam stabilizers in the production of open-cell flexible polyether polyurethane foam having reduced flammability. The block copolymers are modified with certain silicon-bonded organic groups (e.g., C H CH CH or bicycloheptyl groups) which increase the bulk surface tension of the block copolymers.

Open-cell flexible polyether polyurethane foams are produced commercially from reaction mixtures containing polyurethane-forming reactants, a catalyst for the reaction of the polyurethanetorming reactants to produce the polyurethane, a blowing agent and a siloxanepolyoxyalkylene block copolymer foam stabilizer. Such foams are, to some extent, flammable and are used in applications (e.g., automobile scat cushions and household furniture cushions) where fire creates a hazard. Accordingly, it is desirable to reduce the flammability of such foams.

This invention is based, in part, on the discovery that the siloxane-polyoxyalkylene block copolymers used in producing open-cell flexible polyether polyurethane foam can be modified by the incorporation of certain organic groups therein so as to reduce the flammability of the resulting foam. The organic groups which produce this effect are those which increase the bulk surface tension of the siloxane-polyoxyalkylene block copolymers.

This invention provides a process for producing an open-cell flexible polyether polyurethane foam by reacting and foaming a mixture of (a) polyether polyurethaneforming reactants, (b) a catalyst for the reaction of (a) to produce the polyurethane, (c) a blowing agent and (d) a siloXane-polyoxyalkylene block copolymer foam stabilizer consisting essentially of (A) at least one siloxane block consisting essentially of siloxane units having the formula:

2 wherein a is an integer that has a value from 1 to 3 inclusive, R is a monovalent hydrocarbon group, or a divalent atom or a divalent group that links the siloxane block to a polyoxyalltylene block, said siloxane block containing at least one such divalent atom or divalent group represented by R, and (B) at least one polyoxyalkylene block consisting essentially of oxyalkylene units, the novel feature of which process consists in reducing the flammability of the foam by incorporating in the siloxane block of the block copolymer at least one silox ane unit having the formula:

2 wherein b is an integer that has a value from 1 to 3 inclusive and R is a monovalent organic group that increases the bulk surface tension of the block copolymer. The groups represented by R are present in an amount insufficient to cause collapse of the foam. Each polyoxyalkylene block is bonded to a siloxane block by a divalent atom or a divalent group represented by R in Formula 1.

3,686,254 Patented Aug. 22, 1972 "ice The mixtures used in the process of this invention preferably also contain an organic flame retardant.

The presence of the groups represented by R in the siloxane units represented by Formula 2 in a siloxane polyoxyalkylene block copolymer reduces the flammability of a polyether polyurethane foam produced therefrom. The groups which have this property are those which increase the bulk surface tension of the block copolymer. Without wishing to be bound by any particular theory, it appears that groups which increase the bulk surface tension of the block copolymer also increase the bulk surface tension of the parent siloxane. For purposes of this invention, the parent siloxane corresponds in composition to the siloxane blocks except that the parent siloxane contains a group (e.g., hydrogen) having little or no effect on the bulk surface tension of the siloxane in place of the divalent atom or divalent group represented by R in Formula 1. The bulk surface tension of the block copolymer and the parent siloxane is measured by conventional means (e.g., using a du Nouy Surface Tensiometer).

It has been found that, when a high proportion of the siloxane units present in the siloxane blocks of the block copolymers used in this invention are represented by Formula 2, they may raise the bulk surface tension of the copolymer to the extent that the foam collapses. Hence, such units should be present in an amount insufiicient to cause collapse of the foam. Preferably, the relative amount of units represented by Formula 2 is such that the bulk surface tension of the block copolymer is increased by from 1 to 6 dynes per centimeter at 25 C. Copolymers containing siloxane blocks having from 50 to mol percent of units represented by Formula 1 above and from 5 to 50 mol percent of units represented by Formula 2 are preferred, especially where R in Formula 2 has a relatively high molecular weight.

The specific type of unit represented by Formula 2 above incorporated into a block copolymer in order to decrease the flammability of the resulting foam will depend on the desired basic structure of the siloxane block. By way of illustration, when it is desired to provide a block copolymer having siloxane blocks containing a major amount of dimethylsiloxane units (Me SiO), a minor amount of methylethylsiloxane units can be incorporated into the siloxane blocks. The latter units increase the bulk surface tension of the block copolymer and decrease the flammability of foams produced using block copolymers containing such siloxane blocks as foam stabilizers. Obviously, when it is desired to provide block copolymer having siloxane blocks containing a major amount of methylethylsiloxane units, different siloxane units having the desired bulk surface tension increasing property must be incorporated into the block. In general, when the monovalent hydrocarbon groups represented by R in Formula 1 are methyl groups, the desired increase in bulk surface tension can be achieved by incorporating into the siloxane block units represented by Formula 2 wherein R are alkyl groups containing at least two carbon atoms aryl groups, cycloalkyl groups, the aralkyl groups, the bicycloheptyl groups, the alkylidene-substituted bicycloheptyl groups, the epoxy-containing monovalent hydrocarbon groups and the halogenated derivatives of the aforementioned groups. These groups preferably contain no more than 12 carbon atoms. Illustrative of such R groups are the chloromethyl, chloropropyl, bromobutyl, cyclohexyl, phenylethyl, phenylpropyl, ethylidcne-norbornenyl, dibromoethylidenenorbornenyl, beta-epoxycyclohexyl and gamma-glycidoxypropyl groups.

The chemical bond between the siloxane block and the oxyalkylene block in the block copolymers used in this invention can be provided by any suitable divalent atom or divalent group [R in Formula 1 above] such as the following: O-, S, NR-, R R

Illustrative of the monovalent hydrocarbon groups that are represented by R in Formula 1 are the alkyl groups (for example, the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-octyl, decyl, dodecyl groups), the cycloalkyl groups (for example,

the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cy- 1 cloheptyl groups), and alkenyl groups (for example, the vinyl, allyl, crotyl, S-butenyl, 1,3-butadienyl, allenyl groups), the cycloalkenyl groups (for example, the cyclopentenyl, cyclohexenyl groups), the alkynyl groups (for example, the ethynyl, propargyl groups), the aryl groups (for example, the phenyl, naphthyl, phenanthrenyl, anthracenyl groups), the aralkyl groups (for example, the benzyl, Z-phenethyl, 2-phenyl propyl, cumyl groups), the alkaryl groups (for example, the tolyl, t-butylphenyl, styryl, cyclohexylphenyl groups).

Illustrative of the divalent hydrocarbon groups represented by R in Formula 1 and R above are the alkylene groups (e.g., the methylene, ethylene, propylene, 1,2-, 1,3-propylene and butylene groups), the arylene groups (e.g., the ortho, meta and para phenylene groups) and the alkenylene groups (e.g., the CH=CH,

CH CI-]1=CHCH and groups).

In the above formulas, the symbols representing the numbers and types of groups need not have the same meaning at each occurrence throughout the composition. For example, in a given block copolymer having groups represented by Formula 1 above, some of such groups can be dimethylsiloxane groups while other of such groups can be methylsiloxane groups and/or trimethylsiloxane groups. Of course, at least one group represented by Formula 2 must be present.

The siloxane units represented by Formula 2 above can be incorporated in the block copolymers used in the process of this invention by any suitable method. By one method (Method 1), a mixture containing (A) a silane having one or more hydrolyzable groups, a group reactive with a reactive polyoxyalkylene polymer and one or more monovalent groups bonded to silicon and (B) a silane having one or more hydrolyzable groups and a group represented by R in Formula 2 bonded to silicon can be cohydrolyzed and co-condensed to produce a siloxane which can then be reacted with a reactive polyoxyalkylene polymer to produce the block c0- polyrner. By a second method (Method 2), a siloxane containing monovalent groups represented by R in Formula l and groups reactive with both (I) a reactive polyoxyalkylene polymer and (II) a precursor for the groups represented by R in Formula 2 can be reacted with (I) and (II) to produce the block copolymer. In the latter illustration, (1) and (II) can be reacted with the siloxane concurrently or in any sequence. By a third method (Method 3), a siloxane containing silicon-bonded R groups and groups reactive with a reactive polyoxyalkylene polymer can be equilibrated with siloxanes containing silicon-bonded R groups to produce a siloxane containing these various groups. The latter siloxane can then be reacted with a reactive polyoxyalkylene polymer to produce the block copolymer. By way of illustrating Method 1, a mixture of methyldichlorosilane (MeSiHCl dimethyldichlorosilane (Me SiCl trimethylchlorosilane (Me SiCl) and beta-phenylethyl(methyl) dichlorosilane (C H CH CH SiMeCl can be cohydrolyzed and co-condensed to produce a siloxane which then can be reacted with an alkenyl endblocked polyoxyalkylene polymer in the presence of an addition catalyst (e.g., chloroplatinic acid) to produce the block copolymer. By Way of illustrating Method 2, a siloxane having the formula Me SiO(Me SiO) (MeSiHO) SiMe where r and s are integers can be reacted with an alkenyl endblocked polyoyalkylene polymer and an aralkenyl compound (e.g., styrene or alpha-methyl styrene) in the presence of an addition catalyst to produce the block copolymer. By way of illustrating Method 3, a siloxane having the formula Me SiO(Me SiO),(MeSiHO) SiMe where r and s are integers can be equilibrated with a cyclic siloxane having the formula (aralkyl-SiMeOh in the presence of an equilibration catalyst to produce a siloxane which then can be reacted with an alkenyl endblocked polyoxyalkylene polymer in the presence of an addition catalyst to produce the block copolymer. Still other methods for incorporating groups represented by Formula 2 in the copolymers will be apparent to those skilled in the art.

As noted above, the block copolymers employed in the process of this invention can be produced by reacting a reactive polyoxyalkylene polymer with a siloxane having a group reactive with the polyoxyalkylene polymer. In such reactions, the nature of these reactive groups determines the structure of the divalent atom or divalent, organic group represented by R in Formula 1 above. These reactions can be illustrated by the following equations:

ECOSlEi-Hq wherein R is hydrogen, an alkyl group, or an acyl alltylene block contains at least four oxyalkylene groups.

Illustrative of the oxyalkylcne groups that are represented by Formula 3 are the oxyethylene, oxypropylene, oxy-1,4-

butylcne, oxy-LS-amylene, oxy-2,2-dirnethyl-1,3-propyl- H ene, oxy-LlO-decylene groups and the like. The oxyalkylenn portion of the copolymers can contain more than one of the various types of oxyalkylene groups represented by Formula 3. By way of illustration, the oxyalkylene blocks can contain only oxyethylene groups or both oxyethylene and oxypropylene groups, or other combinations of oxyethylene groups and the various other types of oxyalkylene groups represented by Formula 3.

The oxalkylene portion of the block copolymer employed in this invention can contain various organic and end-blocking or chain terminating groups. By way of illustration, the oxyalkylene blocks can contain such endbloclting groups as the hydroxy group, the aryloxy group (such as the phenoxy gro p), the alkoxy groups (such as the methoxy, ethoxy, propoxy and butoxy groups), acyloxy groups (e.g., the acctoxy and propionyloxy groups), aralkoxy groups, carbamyloxy groups, carbonate groups (e.g., OCOOCH and the like. Also, a single group can serve as an end-blocking group for more than one oxyalkylene chain. For example the giyceroxy group,

on-zonc m o l i I can serve as an end-blocking group for three oxyalkylene chains. Trihydrocarbylsiloxy groups (e.g., trimethylsiloxy groups) can also end-block the oxyalkylene chains. Preferred polyoxyalkylene blocks are those represented by the formula:

wherein R'' is hydrogen, an alkyl group, or an acyl group, m has a value from 0 to 100, n has a value from 0 to 100 and m+n has a value from to 200.

Preferred block copolymers for use in the process of this invention are presented by the average formula:

1 t n 'oammo) .renaming (5) wherein Me is methyl R is an alkylene group, an alkylene CO- group (where the free valence of alkylene is attached to the silicon atom) or an alkylene NHCO group (where the free valence of alkylene is attached to the silicon atom), x has a value from 0 to 200, y has a value from 1 to 100, z has a value from 2 to 30, p is 0 or 1 and R", R"", m and n are as defined above for Formulas 2 and 4.

The term block copolymer is used herein to denote a material wherein at least one section ("block) of the molecule is composed of recurring monomeric units of one type and at least one other section (block) of the molecule composed of recurring monomeric units of a different type. The different sections or blocks in the molecule can be arranged in any configuration (e.g., AB, ABA, branched or cyclic). Thus the term block copolymers as used herein includes graft copolymers. The block copolymers used in this invention can be discrete chemical compounds. Usually, however, the block copolymers are mixtures of various discrete block copolymeric species. The block copolymers are usually mixtures due, at least in part, to the fact that the siloxane and polyoxyalkylene reactants used to produce the block copolymers are themselves usually mixtures.

As uscd herein, open-cell" denotes that a flexible foam has interconnecting cells to the extent required to impart adequate breathability for such end uses of the foam as a cushioning material.

The nature of the polyether polyurethane-forming reactants employed in the process of this invention is dietated by the technique (one-shot, prepolymer or quasiprepolymer) used to produce the foam. When the oneshot or one-step technique is used, the reactants are a polyether polyol and an organic polyisocyanate. When the quasi-prepolymer technique is used, the reactants are a prepolymer (formed by reacting an excess of an organic polyisocyanate and a polyether polyol) and a polyether polyol. When the prepolymer technique is used, the re actants are water and an isocyanato-terminated reaction product of a polyether polyol and a polyisocyanate.

The organic flame retardants that can be employed in the process of this invention can be chemically combined in one of the other of the materials used (e.g., in the polyether polyol, the prepolymer or the quasi-prepolymer) or can be a discrete chemical compound. The flame retardants preferably contain phosphorus or halogen or both phosphorus and halogen. Flame retardants of the discrete chemical compound variety include 2.2-dit'bromomethyl)-l,3-propanediol, (ClCH CH O) P(O), 2,3-dibromopropanol, brominated phthalate ester diols (e.g. from tetrabrornophthalic anhydride and propylene oxide), oxypropylated phosphoric acid, polyol phosphites (eg. tris- (dipropylene glyco|)phosphite), polyol phosphonates (cg. bis(dipropylene glycol)hydroxymethane phosphonate), tris(2,3 dibromopropyl)phosphate, tris(l,3-dichloropropyHphosphate, tetrabromobisphenol A, tetrabromophthalic anhydride, 2,4,6-tribromophenol, pentabromophenol, bis(2,3-dibromopropyl) phosphoric acid or salts thereof, tris(1 bromo 3 chloroisopropyl) phosphate, bromo anilines and dianilines, di-polyoxyethylene hydroxymethyl phosphonate, 0,0 diethyl N,N-bis(2-hydroxyethyl)arninomethyl phosphonate, di-polyoxypropylene phenyl phosphonate, di-polyoxyproylene chloromethyl phosphonate, di-polyoxypropylene butyl phosphate,

tris(dichloropropyl)phosphine, tetrachlorophthalic anhydride, chlorendic acid and its anhydride, diallyl chlorendate, tetrabromoethylene, perchlorobicyclopentadiene, 3, 3,3 trichloropropene l, 1,2 dichloro-2,3-epoxypropane, bis(2,3 dibromopropyl)ether of sorbitol, hexachlorobenzene, tris 4(l,3-dioxacylopentyl) methyl phosphite, butyl mono and di acid phosphate, chlorinated maleic anhydride, phosphoramidates, dipentaerythritol phosphite, diethyl phosphite, dipropylene glycol hydrogen phosphite, tristtetramethylcyclobutanediol) phosphite, dimethyl phosphite, ammonium polyphosphate, polyol phosphates, diethyl 2,3-dihydr0propyl phosphonate, dipropylene glycol tetrol diphosphonate, tetrakis(hydroxypropyl)- 2,2-bis(chloromethyl)-l,3-propanediol bis phosphate, dichlorinated adduct of l(ahydroxy-fl-trichloroethyl)dicyclopentadienc, tris-dipropylene glycol phosphite/glycerinepolyoxypropylenetriol adducts, diethyl 1 hydroxyethylphosphonate, polyoxyethylenephenylphosphonate, oxypropylated phosphoric acid, bisthydroxymethyl) phosphinic acid, pentachlorophenylbis(polypropylene glycol)phosphate, oxypropylated melamine, and

N,N,N-tris(Z-hydroxyethyl)ethylenediamine.

Those of the above flame retardants of the discrete chemical compound variety which contain groups reactive with hydroxy or isocyanato groups can be used as starters in producing the polyether polyols or can be reacted with organic polyisocyanates to produce modified polyols or polyisocyanates having chemically combined flame retardant groups. Such modified polyethers and polyisocyanates are useful as reactants in the process of this invention. In such cases, due regard must be given to the possible effect of the functionality of the compound on the other properties (e.g., degree of flexibility) of the resulting foam.

The organic polyisocyanates that are useful in the process of this invention are organic compounds that contain at least two isocyanato groups. Such compounds are well known in the art of producing polyurethane foams. Suitable organic polyisocyanates include the hydrocarbon diisocyanates (e.g., the alkylene diisocyanates and the arylene diisocyanates) as well as known triisocyanates.

As examples of suitable polyisocyanates one can mention 1,2-diisocyanatoethane, 1,3-diisocyanatopropane, 1,2- diisocyanatopropane, 1,4 diisocyanatobutane, 1,5 diisocyanatopentane, 1,6 diisocyanatohexane, bis(3 isocyanatopropyl)ether, bis(3 isocyanatopropyl)sulfide, 1, 7 diisocyanatoheptane, 1,5 diisocyanato 2,2 dimethylpentane, 1,6 diisocyanato 3 methoxyhexane, 1,8- diisocyanatooctane, 1,5 diisocyanato 2,2,4 trimethylpentane, 1,9 diisocyanatononane, 1,10 diisocyanatodecane, 1,6 diisocyanato 3 butoxyhexane, the bis (3- isocyanatopropyl)ether of 1,4 butylene glycol, 1,l1-diisocyanatoundecane, 1,12 diisocyanatododecane, bis(isocyanatohexyl)sulfide, 1,4 diisocyanatobenzene, 2,4 diisocyanatotoluene, 2,6 diisocyanato tolylene, 1,3 diisocyanato-o-xylene, 1,3 diisocyanato-m-xylene, 1,3 diisocyanato-pxylene, 2,4 diisocyanato 1 chlorobenzene, 2,4 diisocyanato 1 nitrobenzene, 2,5-diisocyanato-lnitrobenzene.

The polyether polyols that are useful in the process of this invention are organic compounds containing a plurality of ether linkages and at least two alcoholic hydroxyl groups. The polyoxyalkylene polyols contemplated can be illustrated by the ethylene oxide, 1,2-epoxypropane, and the vicinal epoxy butane adducts of ethylene glycol, propylene glycol, 1,3-dihydroxybutane, 1,4-dihydroxybutane, 2 methyl 2 ethyl 1,3 propanediol, l,5dihydroxypentane, Z-ethylhexanediol-1,3-glycerol, 1,2,4-trihydroxybutane, 1,2,6 trihydroxyhexane, 1,1,l-trimethylolethane, 1,1.1-trimethylolpropane, and the like.

The polyol or polyol mixture employed can have hydroxyl numbers which vary over a wide range. In general, the hydroxyl numbers of the polyols employed in the invention can range from about and lower, to about 120 and higher, preferably, from about to about 80. The hydroxyl number is defined as the number of milligrams of potassium hydroxide required for the complete neutralization of the hydrolysis of the fully acetylated derivative prepared from 1 gram of polyol. The hydroxyl number can also be defined by the equation:

56.lX1000Xf where OH=hydroxyl number of the polyol f=average functionality, that is average number of hydroxyl groups per molecule of polyol m.w.=average molecular weight of the polyol.

The amount of polyisocyanate employed will vary slightly depending upon the nature of the polyurethane being prepared. In general, the total -NCO equivalent to total active hydrogen equivalent (i.e., hydroxyl plus water, if water is present) should be such as to provide a ratio of 0.8 to 1.2 equivalents of -NCO per equivalent of active hydrogen, and preferably a ratio of about 1.0 to 1.1 equivalents of -NCO per reactive hydrogen. As used herein, the term index" denotes the amount of polyisocyanate used as percent of the calculated amount for reaction with total polyol hydroxyl groups and water.

Foaming can be accomplished by employing a small amount of a polyurethane blowing agent, such as water, in the reaction mixture (for example, from about 0.5 to about 5 weight percent of water, based upon total weight of the reaction mixture), or through the use of blowing agents which are vaporized by the exotherm of the reaction, or by a combination of the two methods. All of these methods are known in the art. Illustrative polyurethane blowing agents include halogenated hydrocarbons such as trichloromonofiuoromethane, dichlorodifiuoromethane, dichloromonofluoromethane, dichloromethane, trichloromethane, l,l-dichloro-l-fiuoroethane, l,l,2-trichloro-1,2, Z-trifluoromethane, hexafiuorocyclobutene, octafiuorocyclobutane, and the like. Another useful class of blowing agents include thermally-unstable compounds which liberate gases upon heating, such as N,N'-dimethyl-N,N'-dinitrosoterephthalamide, and the like. The generally preferred method of foaming for producing flexible foams is the use of water or a combination of water plus a fluorocarbon blowing agent such as trichloromonofiuoromethane. The quantity of blowing agent employed will vary with factors such as the density desired in the foamed product. In general, however, it may be stated that for grams of reaction mixture containing an average NCO/ OH ratio of about 1:1, about 0.005 to 0.3 mole of gas are used to provide densities ranging from 30 to 1 pound per cubic foot respectively. The exact amount of blowing agent used can be determined by routine laboratory experimentation.

Catalysts are ordinarily employed in the reaction mixture for accelerating the isocyanate-reactive hydrogen reaction. Such catalysts include a wide variety of compounds such as, for example: tertiary amines such as N,N- dimethyl-2-[Z-dimethylaminoethoxy]ethylamine, trimethylamine, N-methylmorpholine, N-ethylmorpholine, N,N- dimethylbenzylamine, N,N dimethylethanolamine, N,N, N,N'-tetramethyl-1,3-butanediamine, triethanolamine, 1, 4-diazabicyclo[2,2,2]octane, (triethylene diamine), bis(di' methylaminoethyl)ether, and the like; salts of organic carboxylic acids with a variety of metals such as alkali metals, akaline earth metals, Al, Sn, Pb, Sb, Mn, Co, Ni, and Cu, some of the more important of such salts being, for instance, stannous octoate, stannous acetate, stannous oleate, lead octoate, metallic driers such as manganese and cobalt naphthenate, sodium acetate, potassium laurate, calcium hexanoate, and the like; organometallic derivatives of tetravalent tin, trivalent and pentavalent As, Sb and Bi, and metal carbonyl of iron and cobalt.

The tertiary amines may be used as primary catalysts for accelerating the isocyanate-reactive hydrogen reaction, or as secondary catalysts in combination with the abovenoted metal catalysts, in particular, the stannous salts of carboxylic acids or the organometallic tin derivatives. Metal catalysts, or combinations thereof, can also be used as the sole catalysts. The catalysts are employed in small amounts, for example, from about 0.001 weight percent to about 5 weight percent, based on weight of the reaction mixture.

Polyurethane foams are produced in accordance with this invention by any of the conventional processes used to produce polyurethane foams (e.g., the one-shot or one step process or the quasi-prepolymer process). Typically the one-shot process comprises (1) combining at a temperature between about 15 C. and about 50 C. separate mixtures comprising (i) a polyether polyol, the siloxancoxyalkylene block copolymer, a catalyst and blowing agent, and (ii) an organic isocyanate (or mixture of organic isocyanates) and (2) maintaining the combined mixture at a temperature between about 15 C. and about 50 C. until the foaming reaction commences, (3) pouring the foaming reaction mixture into a suitable mold be used (weight percentages are based on the total weight of the mixture, that is, the polyether polyol, polyisocyanate, catalyst, blowing agent and foam stabilizer). There is no commensurate advantage to using amounts of foam stabilizer greater than about 5 weight percent. Preferably,

maintained at between about C. and about 50 C-, D the amount of siloxanepolyoxyalkylene block copolymcr and (4) curing the resulting foam by heating the foam present in the foam formulations varies from about 0.5 at a temperature between about 100 C. and about 150 weight percent to about 2.0 weight percent. C. The heating step (4) described in the preceding It is sometimes convenient to form a mixture containing paragraph is not essential, but heating cures the foamed 10 a minor amount of one of the above-described block coproduct to a stable, tack-free, resin foam capable of suppolymers and a major amount of one or more of the other porting a load within a relatively short period of time (in materials used in producing polyurethane foams in accordthe order of about five minutes to thirty minutes), whereance with this invention. Such mixtures can be stored and as longer times are required X; obtain a cured, tack-fge used in the process when desired. resin at room temperature. 50, t e pouring step r The block copolymers used in the process of this invenis not essential since the mixtures (i) and (ii) can be tion result in the produce of foams having reduced flamcombined and the foaming reaction commenced and commability as compared to foams produced from block copleted in a mold. polymers free of units represented by Formula 2 above. The relative amounts of the various other components Moreover, the use of block copolymers containing units reacted in accordance with the above-described process 00 represented by Formula 2 entails the further advantage for producing polyurethane foams in accordance with this that there is less change in the flammability and breathinvention are not narrowly critical. The polyether polyol ability of the resulting foams with changes in block coand the polyisocyanate, taken together, are present in the polymer concentration, providing greater operating latifoam formulations (reaction mixtures) used to produce tude. High foam breathabilities obtained with these cosuch foams in a ma on amount. The relat ve amounts of polymers have made them useful 1n high density and these two components is the amount required to produce molded foam systems where tight, splitting foam IS a the urethane structure of the foam and such relative problem. amounts are well known in the art. The blowing agent, The polyurethane foams produced in accordance with catalyst and block copolymers are each present in the this invention can be used in the same areas and for the known amount necessary to achieve the function of the same purposes as conventional flexible polyether polyurecomponent. Thus, the blowing agent is present in a minor thane foams (e.g., they can be used as cushioning maamount suflicient to foam the reaction mixture, the catterials for seating and for packaging delicate objects, and alyst is present in a catalytic amount (i.e., an amount sufas gasketing material). ficient to catalyze the reaction to produce the urethane The following examples illustrate the present invention: at a reasonable rate) and the block copolymer is present In the following examples, the siloxane-polyoxyalkylene in a foam-stabilizing amount (i.e., in an amount sufficient block copolymers used in the process of this invention (Coto stabilize the foam). polymers I to XIII inclusive) and the siloxane-polyoxy- Thus the amount of the siloxane-polyoxyalkylene block alkylene block copolymers used for purposes of comparicopolymer employed as a foam stabilizer in this invention son (Copolymers A to G inclusive) have the following can vary over wide limits. From about 0.2 weight percent composition: to 5 weight percent or greater of the block copolymer can COMPOSITION OF COPOLYMERS Copolymer Formula I- D" I MDHD'TD'HJM CnllgCzHqSl'Mt'O II M mn'e 'hzM clout MteO IILH hlD42l)'7D"n0l\I ClCil t i [00 1v.-. MD'sD"mM cnnsisteo v MD DuD'wM C' H5C1II S1'MeO v1 Mo DuW M oomcncmocnnsnm v11 MD' Dfi M (0,119,310

V111 MDNDBDWQM SiMe 011 51117 Br Br IX MDnslJ'glY'guM sun-o X MDMD'MIWQM otu o msuuno XI Mnsril u l)"glvl CulisCzllqSiMnO XII iuoao' owm (16inch(ounomsimo X111 ivnmo' nmttn otutoutmuzou snuto A Mmnnnmsi ctutouusmieo n lvm o' nmm R SiMeU c Mnaoflnw u tozutonmoiocmotnocnnsmto 1) MmD'um CtClhSiMeO l c i 7.. G i MD D'nUmM I In the formulas, the symbols have the following meanings: M denotes the Mm' it'lts group; D denotes the Mi Sit) group; 1) denotes the group MnOtCfllstJmtlC ll.tttl ut ll di- In all cases, the block copolymers were produced from allyl and methoxy endblocked polyethers. Such polyethers contain up to 10 mol percent of allyl and hydroxyl endblocked polyethers as impurities. In some cases ,(i.e., in the case of the polyethers used to produce Copolymers II, III, IV, VII to XI, A, C, D, and F), any such hydroxyl groups were converted to acetoxy endblocking groups by reaction with excess acetic anhydride at about 140 C. followed by volatilization of the excess anhydride and by product acetic acid. Accordingly, the block copolymers produced from the polyethers contained up to 10 mol percent OH or A endblocking groups and at least 90 mol percent methoxy endblocking groups on the polyoxyalkylene blocks. For convenience, the block copolymers are depicted in the formulas appearing above as though all the endblockers on the polyoxyalkylene blocks are methoxy groups.

The bulk surface tension measurements indicated in the following examples were obtained with a DuNouy Surface Tensiometer. Foam breathabilities were obtained as described in R. E. Jones and G. J. Fesman in he Journal of Cellular Plastics, volume I, No. 1, January 1965.

Examples 1 to 8 below illustrate the preparation of the novel siloxane-polyoxyalkylene block copolymers useful in the process of this invention.

EXAMPLE 1 A hydrosiloxane was prepared by equilibration of a fluid of average composition (127.1 g.), a fluid of average composition Me SiO MeHSiO) SiMe (16.1 g.), Me SiO cyclics (101.0 g.) and Me SiOSiMe (5.8 g.) using an acid catalyst. Contact time was about ten hours at 25 C., at which time a constant viscosity of 159 centistokes had been reached. When a sample of this fluid was treated with KOH in water/ethanol 23.6 cubic centimeters of hydrogen gas per gram were liberated. The fluid had the average structure A mixture of this hydrosiloxane (14.5 g., 0.015 mole of SiH), a polyether of average structure MeO (C H O) 29 C H O) CH CH=CH (60.5 g., 0.018 mole of allyl), toluene (32 g.) and chloroplatinic acid (25 parts per million Pt based on reactants) was heated rapidly to 90 C. and stirred ten minues. All Sil-I had reacted. Sodium bicarbonate (1 g.) was added, the reaction mixture sparged with nitrogen to 130 C. and filtered. The product, a clear amber liquid, had the average structure:

Me SiO(Me SiO) ,[MeO (C H O) 2g (CQHO C3H5SiMeO] 5CH5C2H4SIMO SiMCg This copolymer is referred to herein as Copolymer V. In

this example and in the following examples, g." denotes grams and Me denotes methyl.

EXAMPLE 2 A solution of a hydrosiloxane of composition Me3SiO(Me2SiO)9g(MHSi-O)34SIMC3 (38.1 g., 0.14 mole of SiH) in toluene (200 g.) was heated to 75 C. chloroplatinic acid parts per million platinum based on reactants) added, then a polyether of composition MeO(C H (C H O) CH CH CH g., mole of allyl) was added dropwise at 7592 C. The rate of addition was such that the reaction mixture remained clear. A solution of alpha-methylstyrene (20.0 g., 0.17 mole) in 25 g. of toluene, containing chloroplatinic acid (50 parts per million platinum based on reactants), was added dropwise to the solution of siloxane-polyether copolymer at C. over a period of fifteen minutes. After five hours at this temperature all but a trace of the SiH had reacted. Sodium bicarbonate (2 g.) was added and the reaction mixture sparged with nitrogen at 140 C. to remove solvent and excess alpha-methylstyrene. The product was a liquid with a viscosity of 4,620 centistokes at 25 C., and had the following average structure:

Measio z 9e a a 29 2 4 20 5 Me 2 SiMC3 This copolymer is referred to herein as Copolymer XII." This copolymer was tested under the same conditions as those in Table I, except that the burning test was ASTM D1692-59T, which is similar to ASTM D-l692-67'I but less stringent. In the -59T test the burner is extinguished when the foam strip has burned one inch. Rise was 7.9 inches, breathability 3.9 ft. /min. and burning extent only 1.23 inches. Under the same conditions for a copolymer of composition rise was 8.2 inches, breathability 1.8 ftP/min. but foam burning extent was 2.56 inches. This copolymer is referred to herein as Copolymer E.

EXAMPLE 3 A mixture of (EtMeSi0) (90.0 g.), a fluid of composition Me SiO(MeHSiO) SiMe (6.3 g.), Me SiOSiMe (2.8 g.) and concentrated sulfuric acid (2.0 g.) was stirred 16 hours at room temperature. After neutralization with sodium bicarbonate the reaction mixture was filtered. The product filtrate was a colorless fluid with a viscosity of 102 centistokes at 25 C. and had the following average composition:

Me SiO(EtMeSiO) MeHSiOhSiMe A mixture of this hydrosiloxane (14.6 g., 0.015 mole of SiH), a polyether of composition MeO(C3H50) CH CH CH (76 g., 0.02 mole of allyl), toluene (45 g.) and chloroplatinic acid (25 parts per million platinum based on reactants) was heated at 90 C. for about fifteen minutes. All SiI-I reacted. Sodium bicarbonate was added, the reaction mixture sparged at 130 C. and filtered. The liquid filtrate was a clear, liquid product having the following average composition:

This copolymer is referred to herein as Copolymer IV.

EXAMPLE 4 Chloromethylmethyldichlorosilane, ClCH SiMeCI (131 g., 0.8 mole) was added dropwise to a mixture of water (288 g., 1.6 mole) and diisopropyl ether (200 g.) at 20- 40 C. After a light nitrogen sparge sodium bicarbonate was added incrementally until the reaction mixture was neutralized, then the mixture filtered. More sodium bicarbonate (10 g.) was added and also anhydrous sodium sulfate (10 g.), followed by sparging at C. and filtration. Clear chloromethylmethyl hydrolyzate (68 g., 78% yield) was obtained.

A mixture of this chloromethylmethylsiloxane (12.0 g., 0.11 mole of ClCH SiMeO), Me Si()(MeHSiO) SiMe (2.1 g., 0.034 mole of SiH), cyclic Me SiO (17.5 g., 0.24 mole of Me SiO), Me Si0Me (0.9 g.) and concentrated sulfuric acid (1.0 g.) was stirred 16 hours at 25 C. The equilibrate was stirred an hour with sodium bicarbonate (7 g.) and filtered. The product was a clear, colorless liquid which by alkaline analysis gave 27.4 cubic centimeters of hydrogen per gram. It had the following composition:

A mixture of this hydrosiloxane (12.9 g, 0.016 mole of Sil-l), a polyether of composition MEO(C3HBO)29(C2H40)2()CH2CH:CH2 (69.1 g., 0.018 mole of allyl), toluene (40 g.) and chloroplatinic acid (25 parts per million platinum based on reactants) were heated at 90 C. until all SiH had reacted. The product was a liquid copolymer having the following composition: M 3 2 )42[ 3 6 )29( 2 4 )2D C H SiMCO]1(CICH2SiM6O)2 SiMC This copolymer is referred to herein as Copolymer III."

EXAMPLE 5 A mixture of cyclic siloxane of composition [(ClC H SiMeO) (Me SiO) (74.2 g., 0.21 mole of [(ClC H SiMeO) (Me Si)a]x, cyclic Me SiO (16.7 g., 0.22 equivalent),

Me SiO(MeHSiO) SiMe (6.3 g., 0.10 equivalent of SiH), Me SiOSiMe (2.8 g.) and concentrated sulfuric acid (2.5 g.) was stirred 16 hours at room temperature. The equilibrate was neutralized with sodium bicarbonate and filtered. By analysis the colorless liquid product contained one equivalent of SiH per 949 grams. The composition was:

A mixture of this chloropropyl-modified fluid (14.5 g., 0.015 equivalents of SiH), the polyether of Example 1 (60.5 g., 0.018 equivalents of allyl), toluene (35 g.) and chloroplatinic acid (35 parts per million platinum based on reactants) were heated at 90 C. until all silanic hydrogen had reacted. Sodium bicarbonate was added, solvent sparged off with nitrogen and the mixture filtered. The product copolymer had a viscosity of 2878 centistokes and had the following composition:

Me SiO(Me SiO) ;[McO(C H O) (C H O) caH si g( SiMe This copolymer is referred to herein as Copolymer II.

EXAMPLE 6 A mixture of (Et SiO) (90.0 g., 0.30 mole),

Me SiO MeI-ISiO) SiMe (6.3 g., 0.1 mole of SiH), Me SiOSiMe (2.8 g.) and concentrated sulfuric acid (2.0 g.) were stirred 16 hours at room temperature, neutralized with sodium bicarbonate and filtered. The product had a viscosity of 218 centistokes at C. It had the following composition: Me SiO(MeHSiO) (Et SiO) SiMe A copolymer was prepared by heating a mixture of this SiH fluid (14.6 g., 0.015 mole of SiH), the polyether of Example 1 (60.4 g., 0.018 mole of allyl), toluene (120 g.) and chloroplatinic acid parts per million platinum based on reactants) until essentially all SiH had reacted. Sodium bicarbonate was added, the reaction mixture sparged with nitrogen and filtered. A liquid copolymer was obtained which had the following composition: MQ-gSiO[MeO(C3H50)2g(C2H40)2o C H SiMcO] (Et SiO) SiMe This copolymer is referred to herein as Copolyrner VII."

EXAMPLE 7 The polyether of Example 1 (59.7 g., 0.014 mole of allyl) containing chloroplatinic acid (75 parts per million platinum based on reactants) was added drop-wise to a solution of a hydrosiloxane of composition MC SiO(M2SiO)g (MeHSi0)34SiM3 (15.3 g. 0.056 mole of SiH) in toluene (125 g.) containing chloroplatinic acid (75 parts per million platinum based on reactants) at 85 C. During the addition the rate was such that the reaction mixture remained clear. Ethylidenenorbornene (6.2 g., 0.052 moles) was added and the reaction temperature maintained at about C. After three hours reaction of SiI-I was complete. Sodium bicarbonate was added, the mixture sparged with nitrogen and finally filtered. The clear liquid copolymer had a viscosity of 5340 centistokes at 25 C. It had the following composition:

M6 310 MC SiQ 96 MEO (C H O 29 2 4. zo a a l a (CH CH C H SiMEO SiM This copolymer is referred to herein as Copolymer IX.

EXAMPLE 8 To the ethylidenenorbornene modified copolymer of Example 7 (10.0 g., 0.008 mole of ethylidene groups) in 60 milliliters of carbon tetrachloride was added dropwise bromine (2.0 g., 0.013 mole of Br in 20 milliliters of carbon tetrachloride at room temperature. During most of the addition a yellow color initially formed, quickly faded after each incremental addition. Finally the yellow color persisted, indicating saturation of the double bond. Sodium bicarbonate (2 g.) was added, and also having a viscosity of 660 SUS. (8.1 g.), the latter to increase the volume for more convenient handling of the product during processing. The mixture was sparged with nitrogen to 100 C. and filtered. The product was a liquid copolymer, clear and light yellow, which had the following composition:

This copolymer is referred to herein as Copolymer VIII. Examples 9 and 10 below, show the properties of foams produced in accordance with the process of this invention as compared to others foams.

The foams were produced from the following materials:

Parts Material by wt Grams Polyether polyol having a hydroxyl number of 56 produced by reacting glycerol and propylene oxide 1 D0 35 Tris(beta-chloroethyl)phosphate (flame rotardant) 10 35. 0 Water 4. 0 14 N. N -dlmethyI-2-[dirnethylaminoethoxy] ethylarntne (catalyst) 0 l 0. 3 Stannous oetoate (catalyst) t) 4 1.4

A mixture of 80 wt.percant 2, 4-toly1e|1c diisocyanate and 20 wt.-percont 2, 6-tolylene diisocyunate. Ether solvent solution of block copolymer I 1 108 index.

2 In all cases the block copolymer was used in the form of a solvent Solution containing 55 Wt.-p0rcent block copolymer and 45 wt..per(-ent 01 an ether solvent mixture consisting 0100 NL'DBICOIILCi HQO[(321140)]1 (CEiHuOhH and 10 wt.-pcrccnt CQHWCQUAO (C2H40) 0.51i.

3 1.2 in Example 9; as indicated in Example 10.

The foams described in the following examples were prepared as follows:

(g) Add 1.12 cubic centimeters of catalyst# using a cc.

syringe.

(h) Mix 8 seconds, then without stopping drill press, add rapidly 179.5 grams of the mixture of diisocyanates. Continue agitation for 7 seconds.

(i) After the mixing cycle pour into a 12'' x 12" x 12" parchment lined cake box supported by a wooden mold.

(j) Allow foam to rest in wooden mold for at least 3 minutes. This is to avoid the dense ridge that will appear if the cake box is removed from the wooden mold when the foam is green.

(k) Cure 15 minutes at 130 C.

(1) Cut foam and measure rise, breathability, and burning extent.

The terms "rise," burning extent and breathability used in Examples 9' and 10 below have the following meanings: amine, tin.

Rise" denotes the foam height. Rise is directly proportional to surfactant potency.

Burning Extent" denotes the burned length of a test specimen of foam measured in accordance with ASTM D-l692-67T. The flammability of a foam is proportioned to its burning extent as measured by this test.

Breathability" denotes the porosity of a foam and is roughly proportional to the number of open cells in a foam. Breathability is measured as follows: A 2" x 2" x 1" piece of foam is cut from near the center of the bun. Using a Nopco Foam Breathability Tester, Type GP-2 Model 40GD10, air is drawn through the 1" portion at a pressure differential of 0.5 inch of water less than atmospheric pressure. The air flow is parallel to direction of original foam rise. The degree of openness of the foam (or foam breathability) is measured by air flow and is designated as standard cubic feet per minute.

EXAMPLE 9 The burning extent, rise and breathability of foams produced using several block copolymers employed in the process of this invention (Copolymers I through IX) and foams produced using several other copolymers (Copolymers A through E) were measured. The results are shown below:

Burning extent: Risa Breathahllity Copolymer (inches) (inches) (fa /min) Foam col psed 2. 02 8. 0 0. 2 2. 17 7. 9 0. 2

Foam collapsed 4. 01 7. 9 2. 2 5 7. 9 1. 2

The above results illustrate that descreased flammability (decreased burning extent) of foams i achieved in accordance with the process of this invention without impairment of rise and breathability.

EXAMPLE 10 The burning extent and breathability of foams produced using two block copolymers employed in the process of this invention (Copolymers X and XI) and of foam produced using two other copolymers (Copolymers E and F) were measured at three copolymer concentrations. The results obtained are as follows:

Burning extent at three Breathability at three Copolymer cone. cone.

C0110 0.6 1.2 2.0 0.6 1.2 2.0 2.1 2.0 1.9 3.0 2.0 2.1 XI 2.0 1.8 1.6 3.3 2.9 2.1 E 2.8 3.8 5.0 3.4 2.4 1.0 F 2.7 3.4 4.3 4.2 1.8 0.7

The above results illustrate that the foams produced using Copolymers X and XI were lass flammable (decreased burning extent) and exhibited less change in burning extent and breathability with concentration than foams produced with Copolymers E and F.

EXAMPLE 1 1 The bulk surface tension of the parent siloxanes of some of the above-described copolymers and of some of the copolymers themselves were as follows:

Block copolymer Parent siloxane bulk surface bulk surface Copolymer tension 1 tension 1 I 23. 6 II 23. 9 22. 9 III 20. 9 23. 1

1 Dynes/cm. at 25 C.

What is claimed is: 1. A siloxane-polyoxyalkylene block copolymer represented by the average formula,

SiMe;

where Me is as aforesaid and R is an organic radical selected from the group consisting of chloromethyl, chloropropyl, ethylidene-bicyclo[2.2.1]hepty1 and a dibromo derivative of said ethylidene-bicyclo[2.2.1]heptyl radical; R" is hydrogen, an alkyl group, an aralkyl group, or an acyl group; m has a value from 0 to 100, n has a value from 0 to 100, and the sum m-l-n has a value from 10 to 200.

2. A siloxane-polyoxyalkylene block copolymer as defined in claim 1 wherein R is said ethylidene-bicyclo- [2.2.1]heptyl radical.

3. A siloxane-polyoxyalkylene block copolymer as defined in claim 1 wherein R is said dibromo derivative of said ethylidene-bicyc1o[2.2.1]heptyl radical.

4. A siloxane-polyoxyalkylene block copolymer as defined in claim 1 wherein R"" is a methyl group.

5. A siloxane-polyoxyalkylene block copolymer as defined in claim 1 wherein 2 has a value of one and each of said alkylene groups has no more than four carbon atoms.

6. A siloxane-polyoxyalkylene block polymer having the average formula,

Me;SiO(Me SiO).(MeSiO), MoSlO SiMe CaHsOl MQO(C;H4 )II\(CI G )\163 M]! wherein: Me is methyl; x is a positive number having a value up to 200; y has a value from 1 to 100; 2 has a value from 2 to 30; m has a value from 0 to 100, n has a value from 0 to 100, and the sum m+n has a value from 10 to 200.

References Cited UNITED STATES PATENTS 3,271,331 9/1966 Ender 260-4482 B 3,272,762 9/1966 Ibbotson et a1. 260448.8 R 3,342,766 9/1967 Huntington 260448.2 B

TOBIAS E. LEVOW, Primary Examiner P. F. SHAVER, Assistant Examiner US. Cl. X.R.

UNITED sums PATENT OFFICE CERTIFICATE OF CORRECTION Patent NO- 3, Issue Date August 22,

Invgn tor a) Edwa I'd L. Morehouse It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 52, after "provide read a 1 line 61, after "atoms" read Column 3, line 5, -R should read R- lines 36-37, phenanthrenyl, anthracenyl" should read phenanthry l, anthryl line 38, 2-phenethyl" should read 2-phenylethyl line 48, the terminal portion of the formula reading "CH2" should read CH Column 4, line 38, "polyoya lkylene" should read polyoxyalkylene Columns 3-4, in the table, in each of equations (b), (e), (f), (h-l), (i) and (j), each occurrence of "C1" should read Cl Column 5, line 16, after "wherein" in lieu of "R"" is hydrogen, an alkyl group, or an acyl" read R is an alkylene group. Preferably each oxyline 30, after "organic" delete "and". Column 6, line 55, that portion of the formula reading "COH O" should read CH OC Column 8, line 46, (triethylene diamine)" should read ("triethylene diamine") line 56, "carbonyl" should read carbonyls Column 10, line 16,

"produce" should read production in the table, opposite the legend "VI": that portion of the first formula reading "C should read D and the terminal portion of the second formula reading "Me" should read MeO Column 11, line 12, "0A" should read OAc line 21, "he" should read the line 68, that portion of the formula reading "(C H should read (C H 0)2 Column 13, line 21, that portion of the formula reading "Meg" should read Me Column 14, line 42, "others" should read other Column 15, line 1, cc." should read 1 cc Column 16, line 9, "lass" should read less line 71, "polymer should read copolymer Signed and sealed this 30th day of January 1973.

(SEAL) Attest: EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

